Pitch-like compositions



iatented july 15,

111., assignor to Great Lakes Carbon Corporation,Morton Grove, 111.,

a corporation of Delaware No Drawing. Application June 15,

Serial N0. 33,222

'14 Claims. (Cl. 196- 149) This invention relates to a process for converting raw petroleum coke and the like into valuable pitch-like substances. p

Raw petroleum coke and related cokes pro- "duced by the pyrolysis of hydrocarbonaceous liquids in non-catalytic processes is a by-product normally useful only as fuels, or after calcination at high temperatures; in the formation of certain carbonaceous articles such as carbon electrodes, anodes and the like. In many localities petroca1ly a waste product. This inventionprovides a method whereby petroleum coke can'beI con- 'erit'ed' into substances of wide utility. v f 1 According to one specific embodiment the. profusible'coke produced by non-catalytic pyrolysis ofhy droc arbons, said coke'having a volatile content of at least 8%, said volatile content being capable of evolution only upon carbonization; inasuitable high boiling solvent. Y 7 f The raw cokes useful in this process must have a-volatile content of at least 8%"and preferably at least 12%. The volatile content may run as high as 30-35%. The term volatile content. as used herein refers only to that portion of the coke which is capable of evolution'u'pon carbon .i'zationat relatively high temperatures. It does "not: include water or volatile material, e. g. oil which is entrapped, occluded t'o', or' otherwise mechanically held in the coke. j

Therawcoke may be produced in the so-called reaction chambers cracking plants or may be produced by the coking or carbonization of high boiling residues such as Tcra c ked residues, coal 'tar pitches and the like.

of thermal-'non-catalytic mcoke finds little or no utility 'andis prac-.

- 15 lce'ss comprises dissolving a raw, normally n'onasphalt, crude oil, topped-or reduced crude oil,

.Such coke hashe'retofore beenconsidered to be substantially carbon, butit has been found that {it isjessnuauy ,a high molecular weight, solid droearbon mixture in which the volatilecon- Qtehtals contemplated herein is organic and 'forms Lia part of the hydrocarbon structure. In contrast wtoIthe'high melting asphalts which maybe produced by the cracking processor upon steam or air-reduction oi heavy cracked or straight run residues, the .raw petroleum coke is non-fusible. A ltliough it can be deformed at temperatures. of the order of 500 F. by the application *or me- ..chanical pressure, the coke has no Qmelting point .and upon simple heating remains undeformed;

I have discovered thatcoke of this character with a volatile content .of 8 to 35% and which is otherwise substantially infusible can be converted in paints, tile, road surfacing,v etc.

lnhlgh molecular weight-orgarmaments. Those 7? solvents are the most useful'which are essentially aromatic in character, since they dissolvejthe coke in the greatest proportions. Among these are coal'tar oils, anthrac'ene 011, etc! andipitches including special coal tar distillate fractions! Certain aromatic derivatives "including nitrobenzene, m-dinitrobenzene, o-nitrophenolf-onitroanisole, o-nitroaniline, oand m-nitrochlorobenzene, 2, 4, dinitrochlorobenzene, monoand di-nitrotoluene, monoand dienitroxylenes, o-nitrodiphenyl, agnitronaphthaleneraifdothers,

arealso'of great'utility for specialfpurposesjeither alone, in combination with one another, ii, when.

combined in varying percentages with or other hydrocarbon solvents. v

Also useful in this process are 'highjboiling petroleum fractions including. 'lubr'icating'frac tions, cracked andstraight run residuesfasphalts, especially those melting below 220 "F; fiirfur'al extracts of hydrocarb'on' oils including furf'ural extracts of lubricating fractions, and other-sol vent extracts which may be'essentially'aromatic ornaphthenic in characten I j These'solvents are not exactly equivalent either in their-solvent power or in the utility for which the resulting coke solution 'may "be employed. Each mayhave a special utility fordifferent purmane poses. For example, a'solution of raw petroleum coke in coal tar; distillate maybe "o'fparticula'r utility in the'roofing industries and in the manufacture or synthetic boards, fiber boards and other slabsor forms. The'solutions of raw; coke in solvents suchascracked residues, hea'vylubri eating oils, and the like may be of "particular utility as: road oils and as a substitute for asphalt The solvents should in general have a melting and boiling point such that they remain liquid in the range of 300-600 F.'-and boil above about The coke may be taken into solution by comminuting the raw coke, mixing it with the solvent, and heating the mixture with agitation to a suitable temperature until it becomes substantially uniform in character. Depending upon the volatile content of the coke, the temperature employed may vary substantially. With low volatile vcokes comparatively higher temperatures and solvents of greater solvent power should be em:-

..ployed. With high volatile cokesilower temperatures and solvents with a lower solvent power maybe used. I

. The choice of the solvent will dependto' som'e extent upon .the amount of. coke that is to be dissolved, and the properties of the finished article. In general solution temperatures o'f' iiouto Properties of product at room uniform pitch.

650 F. may be employed. Coke may be comminuted to less than 100 mesh, if the higher temperatures are to be used, although larger particles can be dissolved where the volatile content and solvent power of the solvent permits use of lower temperatures. 1

In certain instances the coke may be entirely dissolved so far as can be ascertained. In other instances a large portion of the coke dissolves, generally a major portion. and leaves a minor proportion in the form of a stable suspension of minute particles apparently of microscopic size.- These. particles cannot be filtered out by ordinary methods, nor do they settle out upon long standing.

The solution thus produced may range from a material which is liquid at temperatures of 300 to 500 F. and which is a soft pitch at room temperatures, say 75 to 100 F., to a material which is hard and brittle at room temperature and may be a viscous paste at temperatures of 500 F. or higher.

The following examples'are given to illustrate the invention but should not be construed as limiting it to the exact conditions or materials employed. I

EXAMPLE I A raw Mid-Continent petroleum coke was pulverized to pass a 48 mesh screen. The volatile content of the coke exclusive of water was 23.4%, this being capable of evolution only upon carbonization. The varying percentages ofcoke shown in Table I were mixed with a heavy .coal tar oil at the temperatures indicated, mixing being carried out for a period of four to six hours. It will be observed that in proportions up to 50% of coke, uniform liquid solutions were obtained while at 71% of coke the material was liquid but contained minute particles of undissolved but highly dispersed material.

At room temperature the mixture containing 21% coke was a uniform glossy soft pitch useful in asphalt paints, as road oilor in the preparationof roofing materials such as shingles on as a roofing pitch. At 50% coke concentrationa hard, ductile, glossy pitch was obtained useful as a substitute for high penetration roofing asphalt and in the preparation of tile and the like. At 71% concentration a very hard, brittle, uniform pitch was-obtained which could be used as a binder for briquettingcoal or coke, as a binder in the manufacture of carbon anodes and electrodes, or as a component of many building compositions in which a brittle hard asphalt is desirable.

' Table I V Mixing Formulation Conditions Softening Penetra- Mlx Percent Point tion No. Raw Percent V (Ringandi 77F/l00g/ Petrw Heavy Temp. Time Ball) F sec. lam-n Coal Tar C Hours I on Coke 1 21 79 350=-" '4 I 2 50 I 50 360 5 145 12 3 71 29 3 30' i s 269 I 0.1

Properties of'productat hiiriinghemperature-unifoinl liquid. 7

Properties of product at room pitch.

1 Properties of product at mixing temperature-uniform liquid. 7 mperature uniform glossy medium tempcratureuniform' glossy. soft hard ductile pitch.

, 2 Properties 'o'fproductatmixin temperatfi l q suspension. m mwr y hard, brittle Properties of product at room 'theless in stable suspension.

EXAMPLEII A second series of samples were made with a raw petroleum coke from a Texas crude oil, and having 10.1% volatile content. It was pulverized to pass a 48 mesh screen. The percentages in the solutions and the conditions are'shown in Table II.

Table II V Formulation gg fii g M Softening Penetraix Poin tion No. ggs Percent (Ring and 77F/100g/ Petm Heavy Temp. Time Ball) F 5 sec.

hum Coal Tar "C Hours Oil Coke It will be observed that the products indicated in this example differ materially from those of Example I. The coke was dissolved to a substantially lesser extent. It is useful asa filled asphalt composition used for water proofing and sealing compounds. The sample containing the higher percentages of coke could be used as a. paste or cement for filling cracks and the like. This example illustrates the effect of the decreased volatility on the type of product that can be produced.

It should be borne in mind that thecoke-used in these compositions must have a uniform volatility of not less than 8 to 10% throughoutflthe coke to be treated. In certain coking operations a part of the coke is overheated locally and be comes hard, infusible and insoluble. The volatile content does not refer to an average volatility wherein lumpsof such partially calcined coke of low volatility are contained, since-such low volatile material can neither be dissolved nor dispersed. In selecting the coke care shouldba taken to eliminate suchoverheated portions; v

EXAMPLE III A raw petroleum coke of approximately 30% volatility, but nevertheless having no fusing in the preparation of road surfacing, roofing pitch and .in the preparation of emulsions similar to asphalt emulsions. I

It containeda small percentage of finely divided apparently solid particles which were'never To the mixtureof ExampleIIIwasadded about 5% of a-nitronaphthalene at about 4009.?

5. mixture thus produced was a uniform liquid, indicating that the solvent power of the fuel oil was increased by the addition of the aromatic derivative. Other aromatic compounds such as those hereinbei'ore listed behave similarly.

I claim as my invention:

1. A process which comprises mixing a raw, normally non-fusible coke produced by noncatalytic pyrolysis of highboiling liquid hydrocarbons, with an organic solvent therefor, said solvent being liquid in the range of 300-650 F. and boiling above 500" F., substantially completely dissolving said coke in saidsolvent at a temperature of 300-650 F., and recovering the substantially homogeneous solution thus formed, said coke having a volatile content of at least 8% which is capable of evolution only upon carbonization, the particles of said coke having the further property of being deformable under applied mechanical pressure when heated at about 2. The process of claim 1 wherein the solvent is a petroleum hydrocarbon oil.

3. The process of claim 1 wherein the solvent is a coal tar distillate.

4. The process of claim 1' wherein the solvent is an aromatic hydrocarbon.

5. The process of claim 1 wherein the solvent is a nitro aromatic hydrocarbon.

6. The process of claim 1 wherein the solvent is a coal tar oil.

7. The process of is a hydrocarbon.

8. A pitch-like composition comprising a uniform solution of about 10-75% of raw petroleum coke having a volatile content of at least 8% which is capable of being removed only upon carbonization, and particles of which are capable claim 1 wherein the solvent 11. The composition of claim 8 wherein the solvent is an aromatic hydrocarbon.

12. The composition of claim 8 wherein the solvent is a nitro aromatic hydrocarbon.

13. The composition of claim 8 wherein the solvent is a coal tar oil.

14. The composition of claim 8 wherein the solvent is a hydrocarbon.

HAROLD W. NELSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,657,815 Bates Jan. 31, 1928 1,702,899 Howard Feb. 19, 1929 1,916,333 Rose July 4, 1933 1,925,005 Rose Aug. 29, 1933 2,037,147 Radcliffe Apr. 14, 1936 2,194,574 Snyder Mar. 26, 1940 2,301,322 Reeves et al.- Nov. 10, 1942 I 2,319,326 Jenkner May 18, 1943 2,404,208 Bangham et al July 16, 1946 2,453,641 Reed Nov. 9, 1948 FOREIGN PATENTS Number Country Date 316,897 Great Britain Aug. 6, 1929 

1. A PROCESS WHICH COMPRISES MIXING A RAW, NORMALLY NON-FUSIBLE COKE PRODUCED BY NONCATALYTIC PYROLSIS OF HIGHBOILING LIQUID HYDROCARBONS, WITH AN ORGANIC SOLVENT THEREFOR, SAID SOLVENT BEING LIQUID IN THE RANGE OF 300-650* F. AND BOILING ABOVE 500* F., SUBSTANTIALLY COMPLETELY DISSOLVING SAID COKE IN SAID SOLVENT AT A TEMPERATURE OF 300-650* F., AND RECOVERING THE SUBSTANTIALLY HOMOGENEOUS SOLUTION THUS FORMED, SAID COKE HAVING A VOLATILE CONTENT OF AT LEAST 8% WHICH IS CAPABLE OF EVOLUTION ONLY UPON CARBONIZATION, THE PARTICLES OF SAID COKE HAVING THE FURTHER PROPERTY OF BEING DEFORMABLE UNDER APPLIED MECHANICAL PRESSURE WHEN HEATED AT ABOUT 500* F. 